Polyolefinic molding  composition having improved resistance to thermooxidative degradation and its use for the production of pipes

ABSTRACT

A molding composition is suitable for the production of pipes having improved resistance to thermooxidative degradation when these pipes are in long-term contact with liquids comprising disinfectants having an oxidizing effect. Such molding composition comprises, in addition to thermoplastic polyolefins, a polyoxy compound and/or a polyhydroxy compound as additive in an amount of from 0.01 to 1.0% by weight. In addition, the molding composition can further comprise an unsaturated aliphatic hydrocarbon in an amount of up to 5% by weight. The invention also relates to a process for improving the long-term resistance of water pipes to damage caused by oxidizing disinfectants from the water by use of this molding composition.

This application is the U.S. national phase of International Application PCT/EP2006/004251, filed May 6, 2006, claiming priority to German Patent Application 102005023040.7 filed May 13, 2005, and the benefit under 35 U.S.C. 119(e) of U.S. Provisional Application No. 60/688,397, filed Jun. 8, 2005; the disclosures of International Application PCT/EP2006/004251, German Patent Application 102005023040.7 and U.S. Provisional Application No. 60/688,397, each as filed, are incorporated herein by reference.

The present invention relates to a polyolefinic molding composition which has improved resistance to thermooxidative degradation and is particularly suitable for producing pipes which are in long-term contact with liquids comprising disinfectants having an oxidizing effect.

Molding compositions comprising polyethylene (PE), polypropylene (PP) and poly-1-butene (PB-1) have for many years been used for producing plastic pipes for the distribution of cold and hot water, preferably in buildings.

Although the pipes comprising the plastics mentioned have very good resistance to water, it has been found that their life is severely limited when the pipes come into contact with customary disinfectants which are often added to the water for hygiene reasons. This is important because small amounts of oxidizing substances such as chlorine gas, Na-hypochloride (bleaching liquor), calcium hypochloride or chlorine dioxide are generally added as disinfectants to municipal mains water. Hydrogen peroxide (H₂O₂) or ozone is sometimes also used.

The polyethylene pipes can be uncrosslinked or crosslinked. Crosslinking can be effected by the customary industrial crosslinking processes by means of organic peroxides, grafted vinylsilane esters or by means of high-energy radiation (γ- or β-rays).

It is therefore an object of the present invention to develop a novel molding composition which is based on polyolefins such as polyethylene (PE), polypropylene (PP) or poly-1-butene (PB-1) and retains good processability to produce pipes with an improved stability when these are used for mains water comprising disinfectants having an oxidizing effect.

This object is achieved by a molding composition of the generic class mentioned at the outset, whose distinguishing feature is that it comprises a thermoplastic polyolefin and an amount of from 0.01 to 1.0% by weight, based on the total weight of the molding composition, of an organic polyoxy compound having the general chemical formula:

R—[(CH₂)_(n)—O]_(m)—H

where n is an integer in the range from 1 to 10, m is an integer in the range from 3 to 500 and R is a hydrogen atom or an OH group or an alkyl group which has from 1 to 10 carbon atoms and may bear further substituents such as —OH, —COOH, —COOR, —OCH₃ or —OC₂H₅, or an organic polyhydroxy compound having the general chemical formula:

RO—CH₂—C—(CH₂—OR)₃

where R can be a hydrogen atom or an alkyl group which has from 1 to 5 carbon atoms and may bear further substituents such as —OH, —COOH, —COOR, —OCH₃ or —OC₂H₅, or a combination of the two.

WO 2001/90230 discloses a polyolefin such as PE or PP which comprises polyethylene glycol in amounts of from 5 to 50% by weight as lubricant and is intended to be used, inter alia, for the production of pipes. However, the high additions of polyethylene glycol described there impair the mechanical properties of the polyolefins and are therefore not suitable for the use of pressure-rated water pipes in buildings.

JP-A 09/143,318 (Nippon) describes a process for producing pipes, in which an LLDPE comprising an additive combination of fluoropolymer plus polyoxyalkylene is processed by extrusion and by means of which die dust is said to be avoided.

The molding composition of the invention differs from the prior art in the incorporation of a smaller amount of polyoxy compound or polyhydroxy compound of the abovementioned chemical composition, which despite its presence in such small amounts gives the pipes comprising the molding composition good stability to the oxidizing effects of disinfectants in water over a long time period, which was particularly surprising.

Polyoxy compounds which have been found to be particularly useful are polyethylene glycol, methoxypolyethylene glycol and polypropylene glycol. Preference is given to using polyoxy compounds which have a mean molar mass in the range from 400 to 9000 g/mol. The preferred amounts in which these polyoxy compounds are used are in the range from 0.01 to 0.5% by weight, particularly preferably from 0.1 to 0.3% by weight.

Polyhydroxy compounds which have been found to be particularly useful are pentaerythritol, trimethylolpropane, glycerol, mannitol and sorbitol. The preferred amounts in which these polyhydroxy compounds are used are in the range from 0.01 to 0.5% by weight, particularly preferably from 0.1 to 0.3% by weight.

In a particular embodiment of the invention, the molding composition may comprise additionally an unsaturated aliphatic hydrocarbon compound having the general chemical formula:

R¹—[(CHR²)—CH═CH—CHR³]_(n)—R⁴

where R¹ and R⁴ are each, independently of one another, —H, —CH₃, —OCH₃ or —CH₂OH and R2 and R3 are each, independently of one another, —H, —CH₃, C₂H₅ or C₃H₇.

The amount in which the additional unsaturated aliphatic hydrocarbon compound can be present in the molding composition of the invention is variable and is in the range from 0.1 to 5% by weight, based on the total weight of the molding composition.

As unsaturated aliphatic hydrocarbon compounds, preference is given, according to the invention, to polyisoprene, polyoctenamer or polydecenamer.

Thermoplastic polyolefins which are particularly suitable according to the invention are polyolefins such as PE, PP and PB-1 comprising the homopolymers and the copolymers of these with further olefinic monomers having from 4 to 10 carbon atoms, which can readily be processed by the extrusion technology to produce pipes. Such polyolefins can be prepared by polymerization of the monomers in the presence of suitable catalysts such as Ziegler catalysts, Ziegler-Natta catalysts, chromium comprising Phillips catalysts or single side catalysts such as metallocenes or the like.

The polymerization is carried out at temperatures in the range of from 0 to 200° C., preferred from 25 to 150° C. and more preferred from 40 to 130° C. and under a pressure of from 0.05 to 10 MPa and preferred from 0.3 to 4 MPa. The polymerization may be performed discontinuous or preferred continuous in a single or multiple step process. Thereby it is possible to employ solutionpolymerization or suspensionpolymerization or stirred gas phase polymerization or gas phase fluidized bed polymerization. The artisan is familiar with this technology and with processes of this kind as they belong to the general knowledge.

Molding compositions according to the invention can comprise PE which can be linear or non-linear and may have different densities such as high-density PE (HDPE) or medium-density PE (MDPE) or low-density PE (LDPE) or linear-low-density PE (LLDPE). In a preferred embodiment, the molding composition comprises a PE having a density at a temperature of 23° C. in the range of from 0.93 to 0.965 g/cm³ and a melt index MI_(190/5) in the range of from 0.1 to 2 g/10 min.

Molding compositions according to the invention comprising PP can, for example, be high molecular weight isotactic or syndiotactic homopolymers, random copolymers or block copolymers having a melt index MI_(230/5) in the range from 0.1 to 2/10 min.

Molding compositions according to the invention comprising PB-1 can be, for example, homopolymers or copolymers having a melt index MI_(190/2.16) in the range from 0.1 to 1 g/10 min and a density at a temperature of 23° C. in the range from 0.92 to 0.95 g/cm³.

The molding composition of the invention can further comprise additional additives in addition to the thermoplastic polyolefin. Such additives are preferably heat stabilizers and processing stabilizers, antioxidants, UV absorbers, light stabilizers, metal deactivators, peroxide-destroying compounds, organic peroxides, basic costabilizers in amounts of from 0 to 10% by weight, preferably from 0 to 5% by weight, and also carbon black, fillers, pigments or combinations of these in total amounts of from 0 to 30% by weight, based on the total weight of the mixture.

As heat stabilizers, the molding composition of the invention can comprise phenolic antioxidants, in particular pentaerythrityl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate which is obtainable under the trade name IRGANOX from Ciba Specialities, Germany.

It was especially surprising that the molding composition in terms of the present invention can be processed to give pipes having an extraordinary improved long term stability, if such pipes are exposed to and in continuous contact with chlorinated water. Another highly surprising finding was the high resistance to breakthrough of such pipes in combination with their improved organoleptic.

The following working examples are added to better illustrate the advantages of the new molding composition and especially those of the new pipes prepared therefrom. However, the working examples are by no means intended to cause any restrictions in the scope of the invention.

EXAMPLE 1

A high molecular weight medium-density PE powder having a density of 0.946 g/cm³ and a melt flow index MI_(190/5) of 0.3 g/10 min was admixed with 0.1% of polyethylene glycol having a molar mass of 9000 g/mol, 1% of Vestenamer 8012 and 0.35% of IRGANOX 1330 and pelletized at a melt temperature of 220° C. on a ZSK 53 from Coperion Werner & Pfleiderer GmbH & Co KG. The pellets were processed at a melt temperature of 220° C. on a pipe extrusion unit from Battenfeld to produce pipes having a diameter of 16×2 mm, and these were subsequently crosslinked by means of electron beams. The radiation dose applied was 120 kGy. The degree of crosslinking was determined in accordance with DIN EN 16892 and was 66%.

A creep test in accordance with ASTM F2023 was carried out on the crosslinked pipes at 115° C. in the presence of 4 ppm of chlorine at a load of 1.58 MPa. The time-to-failure achieved is shown in table 1.

EXAMPLE 2

The high molecular weight MDPE powder having a density of 0.946 g/cm³ and a melt flow index MI_(190/5) of 0.3 g/10 min from Example 1 was admixed with 0.1% of polyethylene glycol having a molar mass of 400 g/mol and 0.35% of IRGANOX 1330 and pelletized, extruded to produce pipes having a diameter of 16×2 mm and crosslinked at 120 kGy by means of electron beams. The degree of crosslinking was determined in accordance with DIN EN 16892 and was 64%.

A creep test was carried out on the crosslinked pipes at 115° C. in the presence of 4 ppm of chlorine at a load of 1.58 MPa. The test was carried out in accordance with ASTM F2023. The time-to-failure achieved is shown in table 1.

EXAMPLE 3

The high molecular weight MDPE powder having a density of 0.946 g/cm³ and a melt flow index MI_(190/5) of 0.3 g/10 min from Example 1 was admixed with 0.2% of polyethylene glycol having a molar mass of 400 g/mol and 0.35% of IRGANOX 1330 and pelletized, extruded to produce pipes having a diameter of 16×2 mm and crosslinked at 120 kGy by means of electron beams. The degree of crosslinking was determined in accordance with DIN EN 16892 and was 66%.

A creep test was carried out on the crosslinked pipes at 115° C. in the presence of 4 ppm of chlorine at a load of 1.58 MPa. The test was carried out in accordance with ASTM F2023. The time-to-failure achieved is shown in table 1.

EXAMPLE 4

The high molecular weight MDPE powder having a density of 0.946 g/cm³ and a melt flow index MI_(190/5) of 0.3 g/10 min from Example 1 was admixed with 0.1% of polyethylene glycol having a molar mass of 400 g/mol, 1% of Vestenamer 8012 and 0.35% of IRGANOX 1330 and pelletized, extruded to produce pipes having a diameter of 16×2 mm and crosslinked at 120 kGy by means of electron beams. The degree of crosslinking was determined in accordance with DIN EN 16892 and was 65%.

A creep test was carried out on the crosslinked pipes at 115° C. in the presence of 4 ppm of chlorine at a load of 1.58 MPa. The test was carried out in accordance with ASTM F2023. The time-to-failure achieved is shown in table 1.

COMPARATIVE EXAMPLE

For comparison, a commercial PEXc material Lupolen 4261A Q416 from Basell was extruded to produce pipes having the dimensions 16×2 mm and radiation-crosslinked at 120 kGy. The degree of crosslinking was found to be 63%.

A creep test was carried out on the crosslinked pipes at 115° C. in the presence of 4 ppm of chlorine at a load of 1.58 MPa. The test was carried out in accordance with ASTM F2023.

TABLE 1 Time to rupture in Example No. pressure test, in h Example 1 1186 Example 2 960 Example 3 1459 Example 4 1453 Comparison 524 

1. A polyolefinic molding composition having improved resistance to thermooxidative degradation for the production of pipes, wherein the molding composition comprises a thermoplastic polyolefin and, in addition, an amount of from 0.01 to 1.0% by weight, based on the total weight of the molding composition, of an organic polyoxy compound comprising a mean molar mass, and having a general chemical formula: R—[(CH₂)_(n)—O]_(m)—H where n is an integer in the range from 1 to 10; m is an integer in the range from 3 to 500; and R is a hydrogen atom, an OH group or an alkyl group which has from 1 to 10 carbon atoms, and optionally bears further substituents selected from —OH, —COOH, —COOR, —OCH₃ or —OC₂H₅, or an organic polyhydroxy compound having the general chemical formula: RO—CH₂—C—(CH₂—OR)₃ where R can be a hydrogen atom or an alkyl group which has from 1 to 5 carbon atoms, and optionally bears further substituents selected from —OH, —COOH, —COOR, —OCH₃ or —OC₂H₅, or a combination of the polyoxy and polyhydroxy compounds.
 2. The polyolefinic molding composition according to claim 1 wherein the polyoxy compounds are selected from polyethylene glycol, methoxypolyethylene glycol or polypropylene glycol.
 3. The polyolefinic molding composition according to claim 1 wherein the mean molar mass of the polyoxy compounds is in the range from 400 to 9000 g/mol.
 4. The polyolefinic molding composition according to claim 1 which comprises the polyoxy compounds in an amount from 0.01 to 0.5% by weight.
 5. The polyolefinic molding composition according to claim 1 wherein the polyhydroxy compounds are selected from pentaerythritol, trimethylolpropane, glycerol, mannitol or sorbitol.
 6. The polyolefinic molding composition according to claim 1 which comprises the polyhydroxy compounds in an amount from 0.01 to 0.5% by weight.
 7. The polyolefinic molding composition according to claim 1 which further comprises an unsaturated aliphatic hydrocarbon compound having the general chemical formula: R¹—[(CHR²)—CH═CH—CHR³]_(n)—R⁴ where R¹ and R⁴ are each, independently of one another, —H, —CH₃, —OCH₃ or —CH₂OH and R² and R³ are each, independently of one another, —H, —CH₃, C₂H₅ or C₃H₇.
 8. The polyolefinic molding composition according to claim 7 which comprises the unsaturated aliphatic hydrocarbon compound in an amount from 0.1 to 5% by weight, based on the total weight of the molding composition.
 9. The polyolefinic molding composition according to claim 7 wherein the aliphatic hydrocarbon compound is selected from polyisoprene, polyoctenamer or polydecenamer.
 10. The polyolefinic molding composition according to claim 1 wherein the thermoplastic polyolefin comprises polyethylene, polypropylene or copolymers of polyethylene or polypropylene with further olefinically unsaturated monomers having from 4 to 10 carbon atoms.
 11. The polyolefinic molding composition according to claim 1 which further comprises additives selected from heat stabilizers, antioxidants, UV absorbers, light stabilizers, metal deactivators, peroxide-destroying compounds, or basic costabilizers present in amounts up to 10% by weight.
 12. A process for improving the resistance of pipes to thermooxidative degradation which are in long-term contact with liquids comprising disinfectants having an oxidizing effect, the process comprising extruding into a pipe, a polyolefinic molding composition comprising a thermoplastic polyolefin and, in addition, an amount of from 0.01 to 1.0% by weight, based on the total weight of the molding composition, of an organic polyoxy compound comprising a mean molar mass and having a general chemical formula: R—[(CH₂)_(n)—O]_(m)—H where n is an integer in the range from 1 to 10; m is an integer in the range from 3 to 500; and R is a hydrogen atom, an OH group or an alkyl group which has from 1 to 10 carbon atoms, and optionally bears further substituents selected from —OH, —COOH, —COOR, —OCH₃ or —OC₂H₅, or an organic polyhydroxy compound having the general chemical formula: RO—CH₂—C—(CH₂—OR)₃ where R can be a hydrogen atom or an alkyl group which has from 1 to 5 carbon atoms and optionally bears further substituents selected from —OH, —COOH, —COOR, —OCH₃ or —OC₂H₅, or a combination of the polyoxy and polyhydroxy compounds.
 13. The process according to claim 12, wherein the polyolefinic molding composition further comprises an unsaturated aliphatic hydrocarbon compound having the general chemical formula: R¹—[(CHR²)—CH═CH—CHR³]_(n)—R⁴ where R¹ and R⁴ are each, independently of one another, —H, —CH₃, —OCH₃ or —CH₂OH and R² and R³ are each, independently of one another, —H, —CH₃, C₂H₅ or C₃H₇.
 14. The process of claim 13 wherein the polyoxy compounds or the polyhydroxy compounds are added as an additive to the thermoplastic polyolefins prior to production of the pipes in amounts from 0.01 to 1.0% by weight, based on the total weight of polyolefin plus additive.
 15. The process according to claim 14, wherein an unsaturated aliphatic hydrocarbon is added to the thermoplastic polyolefin in addition to the polyoxy compounds or the polyhydroxy compounds.
 16. The polyolefinic molding composition according to claim 4 wherein the polyoxy compounds are present in an amount from 0.1 to 0.3% by weight.
 17. The polyolefinic molding composition according to claim 6 wherein the polyhydroxy compounds are present in an amount from 0.1 to 0.3% by weight.
 18. The polyolefinic molding composition according to claim 11 wherein the additives are present in an amount up to 5% by weight. 